CA1221864A - High contrast, high resolution deep ultraviolet lithographic resists - Google Patents
High contrast, high resolution deep ultraviolet lithographic resistsInfo
- Publication number
- CA1221864A CA1221864A CA000499173A CA499173A CA1221864A CA 1221864 A CA1221864 A CA 1221864A CA 000499173 A CA000499173 A CA 000499173A CA 499173 A CA499173 A CA 499173A CA 1221864 A CA1221864 A CA 1221864A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- resin
- sensitizer
- diazo
- deep ultraviolet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/0163—Non ionic diazonium compounds, e.g. diazosulphonates; Precursors thereof, e.g. triazenes
Abstract
HIGH-CONTRAST, HIGH RESOLUTION DEEP
ULTRAVIOLET LITHOGRAPHIC RESISTS
Abstract of the Disclosure A lithographic resin for use with deep ultraviolet radiation comprises a weakly acidic resin and an alpha phosphoryl substituted diazo carbonyl compound as a sensitizer.
ULTRAVIOLET LITHOGRAPHIC RESISTS
Abstract of the Disclosure A lithographic resin for use with deep ultraviolet radiation comprises a weakly acidic resin and an alpha phosphoryl substituted diazo carbonyl compound as a sensitizer.
Description
HIGH CONT~AST, HIGH RESOLUTION DEEP
ULTRAVIOLET LITHOGP~PE3IC RESISTS
DESCRIPTION
Technical Field The present invention is concerned with lithographic resists for use with deep ultraviolet light i.e. light of wavelengths below 313nm. In particular it deals with resists of this type which comprise an a~mixture of a weakly acidic resin and a specific type of sensitizer.
Back~round Art U.S. Patent 4,339,522 describes the use of certain Meldrum's diazo compounds as sensitizers for aeep ultraviolet when incorporated in resins.
U.S. Patent 4,522,911 (06/35) assigned to the same assignee as the present application, discloses the use of diazohomotetramic acid compounds as deep ultraviolet sensitizers.
A resist system for use in lithography using deep ultraviolet light must simultaneously possess several characteristics. One, the system must have a sensitivity which allows it to be used at acceptable exposure and development times. Two, the system should have no spectral sensitivity in the longer wavelength regions, that is, above 300nm. When there is no spectral sensitivity in that range, the need for inefficient spectral filtration of the radiation source is eliminated. Three, the formulated system should have an optical absorption consistent with the ability to ~, ~2~ ~a~
generate photoresist images. Four, the system should ; have chemical and physical charclcteristics compatible with micro fabrication proccsses, such as resistance to reactive ion ctching. Finall~, t~l~ sensitizer should have photoproducts t~lat arc trallsparent at the irradiation frequc~cy.
Because of the numerous dern~ ds which such a system must simultzneously meet, the prior art systems all leave something to be desired and fail to meet these stringcnt requirements completely.
D~scription of the Invention . .
According to the present invention lithographic resists for use wit~ deep ultraviolet light comprise a weakly acidic resin and, admixed therewith, a sufficient quantity of a sensitizer which is an alpha phosphoryl substituted diazo carbonyl compound having the formula ~ 2 R - C - C - P-(OR )n (R )2-n where each of Rl, R2 and R3 independently is alkyl or aryl, and n is 0, 1 or 2.
This class of sensitizer, when incorporated into weakly acidic resins, not only satisfies all the previously noted criteria, but also has the additional 2S advantage of producin~ after exposure ketene intermediates which are photostable and remarkably unreactive toward the acidic host resin. This is a particular advantage of the present invention over the prior art. Prior art sensit~zers yielded post irradiation ketenes which react to some extent with the resin to produce base insoluble derivati~es which do not result in rapid dissolution of th~ exposed resis~ film in basic developers. The sensitizer of the present invention ~vercomes this difficulty.
For use in the present invention, the resist formulation includes a sensitizing amount of a compound o~ the type discussed above and a weakly acidic resin, many of which are well-known in the art. They include, for example, novolac resins s~lch as cresol novolac, poly(p-hydroxystyrene) and copolymers of methacrylic acids with esters and imide containing copolymers. In general the sensitizer is preferably used at a concentration in the resin of from about 5 to 50% of the weight of the resin. The sensitizer is admixed with the resin and, upon image-wise exposure of the resin composition to deep ultraviolet radiation, the exposed portions of the composition becomes more soluble in alkaline developer.
When the expression "deep ultraviolet" is used it is meant to mean light of wavelength of less than 313nm.
Particularly, light of wavelength about 254nm is useful in carrying out the present invention.
The phosphoryl substituted diazo carbonyl compounds useful in the present invention are known materials and their syntheses have been described in the literature. See, for example, M. Regtiz et al Chem. Ber.
1969, 102, 2216 and M. Regtiz et al, Chem. Ber. 1978, 111,3068. Examples of preferred compounds include (Diazophenacyl)-diphenyl phosphine oxide, (Diazo-p-tert-butylphenacyl)-diphenyl phosphine oxide, (Diazo-p-chlorophenacyl)-diphenyl phosphine oxide, (Diazo-p-methoxyphenacyl)-diphenyl phosphine oxide, (Diazo-p-.
~L~2~ 4 phenylphenacyl)-diphenyl phosphine oxide and (Diazophenacyl)-dimethyl phosphonate.
Example of Preferred_mbodiment 1.87 grams of the sensitizer (Diazophenacyl)-diphenylphosphine oxide was dissolved in 40mL of a 25%
wt/v solution of a novolac resin in diglyme. Films l.lum thick were prepared by spinnin~ on 1-inch wafers of silicon at 4000 revolutions per minute. The wafers were then baked at 85C for 30 minutes and exposed in contact mode using a quartz mask (254nm, 70mj/cm2). The system was developed using an aqueous alkaline developer. The time to endpoint was approximately one minute. By this process high contrast vertical profile images were obtained.
ULTRAVIOLET LITHOGP~PE3IC RESISTS
DESCRIPTION
Technical Field The present invention is concerned with lithographic resists for use with deep ultraviolet light i.e. light of wavelengths below 313nm. In particular it deals with resists of this type which comprise an a~mixture of a weakly acidic resin and a specific type of sensitizer.
Back~round Art U.S. Patent 4,339,522 describes the use of certain Meldrum's diazo compounds as sensitizers for aeep ultraviolet when incorporated in resins.
U.S. Patent 4,522,911 (06/35) assigned to the same assignee as the present application, discloses the use of diazohomotetramic acid compounds as deep ultraviolet sensitizers.
A resist system for use in lithography using deep ultraviolet light must simultaneously possess several characteristics. One, the system must have a sensitivity which allows it to be used at acceptable exposure and development times. Two, the system should have no spectral sensitivity in the longer wavelength regions, that is, above 300nm. When there is no spectral sensitivity in that range, the need for inefficient spectral filtration of the radiation source is eliminated. Three, the formulated system should have an optical absorption consistent with the ability to ~, ~2~ ~a~
generate photoresist images. Four, the system should ; have chemical and physical charclcteristics compatible with micro fabrication proccsses, such as resistance to reactive ion ctching. Finall~, t~l~ sensitizer should have photoproducts t~lat arc trallsparent at the irradiation frequc~cy.
Because of the numerous dern~ ds which such a system must simultzneously meet, the prior art systems all leave something to be desired and fail to meet these stringcnt requirements completely.
D~scription of the Invention . .
According to the present invention lithographic resists for use wit~ deep ultraviolet light comprise a weakly acidic resin and, admixed therewith, a sufficient quantity of a sensitizer which is an alpha phosphoryl substituted diazo carbonyl compound having the formula ~ 2 R - C - C - P-(OR )n (R )2-n where each of Rl, R2 and R3 independently is alkyl or aryl, and n is 0, 1 or 2.
This class of sensitizer, when incorporated into weakly acidic resins, not only satisfies all the previously noted criteria, but also has the additional 2S advantage of producin~ after exposure ketene intermediates which are photostable and remarkably unreactive toward the acidic host resin. This is a particular advantage of the present invention over the prior art. Prior art sensit~zers yielded post irradiation ketenes which react to some extent with the resin to produce base insoluble derivati~es which do not result in rapid dissolution of th~ exposed resis~ film in basic developers. The sensitizer of the present invention ~vercomes this difficulty.
For use in the present invention, the resist formulation includes a sensitizing amount of a compound o~ the type discussed above and a weakly acidic resin, many of which are well-known in the art. They include, for example, novolac resins s~lch as cresol novolac, poly(p-hydroxystyrene) and copolymers of methacrylic acids with esters and imide containing copolymers. In general the sensitizer is preferably used at a concentration in the resin of from about 5 to 50% of the weight of the resin. The sensitizer is admixed with the resin and, upon image-wise exposure of the resin composition to deep ultraviolet radiation, the exposed portions of the composition becomes more soluble in alkaline developer.
When the expression "deep ultraviolet" is used it is meant to mean light of wavelength of less than 313nm.
Particularly, light of wavelength about 254nm is useful in carrying out the present invention.
The phosphoryl substituted diazo carbonyl compounds useful in the present invention are known materials and their syntheses have been described in the literature. See, for example, M. Regtiz et al Chem. Ber.
1969, 102, 2216 and M. Regtiz et al, Chem. Ber. 1978, 111,3068. Examples of preferred compounds include (Diazophenacyl)-diphenyl phosphine oxide, (Diazo-p-tert-butylphenacyl)-diphenyl phosphine oxide, (Diazo-p-chlorophenacyl)-diphenyl phosphine oxide, (Diazo-p-methoxyphenacyl)-diphenyl phosphine oxide, (Diazo-p-.
~L~2~ 4 phenylphenacyl)-diphenyl phosphine oxide and (Diazophenacyl)-dimethyl phosphonate.
Example of Preferred_mbodiment 1.87 grams of the sensitizer (Diazophenacyl)-diphenylphosphine oxide was dissolved in 40mL of a 25%
wt/v solution of a novolac resin in diglyme. Films l.lum thick were prepared by spinnin~ on 1-inch wafers of silicon at 4000 revolutions per minute. The wafers were then baked at 85C for 30 minutes and exposed in contact mode using a quartz mask (254nm, 70mj/cm2). The system was developed using an aqueous alkaline developer. The time to endpoint was approximately one minute. By this process high contrast vertical profile images were obtained.
Claims (10)
- The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
l. A lithographic resist composition for use with ultraviolet light of less than 313nm wavelength, said composition comprising a weakly acidic resin and admixed therewith a sufficient quantity of a sensitizer which is an alpha phosphoryl substituted diazo carbonyl compound having the formula where each of R1, R2 and R3 independently is alkyl or aryl, and n is 0, 1 or 2. - 2. A composition as claimed in claim 1 wherein the sensitizer is (Diazophenacyl)-diphenyl phosphine oxide.
- 3. A composition as claimed in claim 1 wherein the sensitizer is (Diazo-p-tert-butylphenacyl)-diphenyl phosphine oxide.
- 4. A composition as claimed in claim l wherein the sensitizer is (Diazo-p-methoxyphenacyl)-diphenyl phosphine oxide.
- 5. A composition as claimed in claim l wherein the sensitizer is (Diazo-p-phenylphenacyl)-diphenyl phosphine oxide.
- 6. A composition as claimed in claim l wherein the sensitizer is (Diazophenacyl)-dimethyl phosphonate.
- 7. A composition as claimed in claim 1 wherein the resin is a novolac resin.
- 8. A composition as claimed in claim 1 wherein the resin is p-cresol novolac.
- 9. A composition as claimed in claim 1 wherein the resin is poly(p-hydroxystryene).
- 10. A composition as claimed in claim 1 wherein the resin is a copolymer of methacrylic acid with an ester thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/717,254 | 1985-03-28 | ||
| US06/717,254 US4601969A (en) | 1985-03-28 | 1985-03-28 | High contrast, high resolution deep ultraviolet lithographic resist composition with diazo carbonyl compound having alpha phosphoryl substitution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1221864A true CA1221864A (en) | 1987-05-19 |
Family
ID=24881303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000499173A Expired CA1221864A (en) | 1985-03-28 | 1986-01-08 | High contrast, high resolution deep ultraviolet lithographic resists |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4601969A (en) |
| EP (1) | EP0195986B1 (en) |
| JP (1) | JPS61223837A (en) |
| CA (1) | CA1221864A (en) |
| DE (1) | DE3662317D1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0772798B2 (en) * | 1988-02-17 | 1995-08-02 | テルモ株式会社 | Pattern formation method on substrate |
| US4968582A (en) * | 1988-06-28 | 1990-11-06 | Mcnc And University Of Nc At Charlotte | Photoresists resistant to oxygen plasmas |
| US5114827A (en) * | 1988-06-28 | 1992-05-19 | Microelectronics Center Of N.C. | Photoresists resistant to oxygen plasmas |
| DE3900736A1 (en) * | 1989-01-12 | 1990-07-26 | Hoechst Ag | POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE CONTAINING A MULTI-FUNCTIONAL (ALPHA) -DIAZO- (BETA) -KETOESTER, METHOD FOR THE PRODUCTION THEREOF AND RADIATION-SENSITIVE RECORDING MATERIAL COMPRISING THIS MIXTURE |
| KR950011927B1 (en) * | 1989-12-07 | 1995-10-12 | 가부시끼가이샤 도시바 | Photosensitive composition and resin-encap sulated semiconductor device |
| DE4014648A1 (en) * | 1990-05-08 | 1991-11-14 | Hoechst Ag | POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE AND RADIATION-SENSITIVE RECORDING MATERIAL FOR EXPOSURE WITH DUV RADIATION |
| DE4014649A1 (en) * | 1990-05-08 | 1991-11-14 | Hoechst Ag | NEW MULTIFUNCTIONAL CONNECTIONS WITH (ALPHA) -DIAZO-SS-KETOESTER AND SULPHONIC ACID UNIT UNITS, METHOD FOR THEIR PRODUCTION AND USE THEREOF |
| JP3030672B2 (en) * | 1991-06-18 | 2000-04-10 | 和光純薬工業株式会社 | New resist material and pattern forming method |
| US5908730A (en) * | 1996-07-24 | 1999-06-01 | Tokyo Ohka Kogyo Co., Ltd. | Chemical-sensitization photoresist composition |
| US5945517A (en) * | 1996-07-24 | 1999-08-31 | Tokyo Ohka Kogyo Co., Ltd. | Chemical-sensitization photoresist composition |
| US5876897A (en) * | 1997-03-07 | 1999-03-02 | Clariant Finance (Bvi) Limited | Positive photoresists containing novel photoactive compounds |
| US5866295A (en) * | 1997-03-07 | 1999-02-02 | Clariant Finance (Bvi) Limited | Photosensitive quinolone compounds and a process of preparation |
| KR100508699B1 (en) * | 2001-08-09 | 2005-08-17 | 학교법인 한양학원 | Azo dyes and azo-metal complexes for atomic force microscope lithography |
| KR100620672B1 (en) * | 2002-12-14 | 2006-09-13 | 주식회사 하이닉스반도체 | Photoresist composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3567453A (en) * | 1967-12-26 | 1971-03-02 | Eastman Kodak Co | Light sensitive compositions for photoresists and lithography |
| US3668197A (en) * | 1969-07-22 | 1972-06-06 | Merck & Co Inc | Esters and amides of (diazomethyl) phosphonic acid |
| GB1529552A (en) * | 1977-05-31 | 1978-10-25 | Hercules Inc | Photocrosslinkable polymers |
| US4207107A (en) * | 1978-08-23 | 1980-06-10 | Rca Corporation | Novel ortho-quinone diazide photoresist sensitizers |
| US4339522A (en) * | 1979-06-18 | 1982-07-13 | International Business Machines Corporation | Ultra-violet lithographic resist composition and process |
| DE3126627A1 (en) * | 1981-07-06 | 1983-01-20 | Hoechst Ag, 6000 Frankfurt | POLYVINYLMETHYLPHOSPHINIC ACID, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| US4522911A (en) * | 1983-06-28 | 1985-06-11 | International Business Machines Corporation | Deep ultra-violet lithographic resists with diazohomotetramic acid compounds |
-
1985
- 1985-03-28 US US06/717,254 patent/US4601969A/en not_active Expired - Lifetime
- 1985-12-24 JP JP60289539A patent/JPS61223837A/en active Granted
-
1986
- 1986-01-08 CA CA000499173A patent/CA1221864A/en not_active Expired
- 1986-03-14 DE DE8686103438T patent/DE3662317D1/en not_active Expired
- 1986-03-14 EP EP86103438A patent/EP0195986B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0195986B1 (en) | 1989-03-08 |
| US4601969A (en) | 1986-07-22 |
| JPH0415463B2 (en) | 1992-03-18 |
| DE3662317D1 (en) | 1989-04-13 |
| EP0195986A2 (en) | 1986-10-01 |
| EP0195986A3 (en) | 1987-02-04 |
| JPS61223837A (en) | 1986-10-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |